JPH07308964A - Production of coating sheet - Google Patents

Abstract

PURPOSE:To obtain a good coated sheet by extruding a base material layer of a thermoplastic elastomer to form a sheet and supplying a laminate wherein a urethane resin is integrally formed on an adhesive resin layer to one surface of the sheet while supplying a foam layer to the other surface thereof, and pinchingly compressing the three layers togeher. CONSTITUTION:A surface layer 1 based on a urethane resin is applied to a rear adhesive resin layer 21 to form a sheet like laminate and this laminate is taken up after drying. Next, a thermoplastic elastomer forming a base material layer 3 is extruded in a sheet form to be fed in a molten state so that the adhesive resin layer 21 of the laminate comes to the gap between the base material layer 3 and the surface layer 1. A foam layer 4 is extruded to the other surface of the base material layer 3 in a sheet like form and three layers are fed to the gap between a pair of embossing rolls 51, 52 to be pressed to be taken up as a coating sheet wherein embossing is applied to the surface layer 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a covering sheet.

[0002]

2. Description of the Related Art Conventionally, as such a covering sheet, a sheet obtained by laminating a polyolefin resin foam sheet on a plasticized vinyl chloride resin sheet whose surface is textured has been used. However, a sheet using the plasticized vinyl chloride resin is likely to lose its flexibility over time, and the odor of the plasticizer contained in the material also impairs the comfort during use. The composite of vinyl resin and other materials has a problem in that complicated steps are required due to differences in polarities between resins.

Due to the above-mentioned reasons, recently, for example, a coating in which a polyolefin-based thermoplastic elastomer layer having a textured surface and a foam layer of polyethylene or polypropylene described in JP-B-1-14023 is laminated. Sheets have been proposed. However, JP-B 1-140
The sheet using the polyolefin-based resin elastomer described in JP-A No. 23 has a drawback that the resistance to scratches is impaired by imparting a contact resistance for improving the feel to the surface of the sheet, and embossing or the like. However, there is a mechanical limitation in giving the surface unevenness freely, and it is difficult to give a sufficient matte and suede-like feel.

Further, Japanese Patent Application Laid-Open No. 63-272547 discloses a method of coating an acrylic ester resin through a primer layer in order to impart scratch resistance to such a coating sheet. However, since the above-mentioned surface treatment step is a post-step, it is necessary to reheat the entire laminate to perform embossing, so that it is difficult to sharply reproduce fine uneven patterns.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to eliminate the above-mentioned drawbacks of the conventional method, and has a sufficient matting property and a suede-like good touch, but is also excellent in scratch resistance. Moreover, it is to provide a method for producing a covering sheet that can be attached beautifully along a shape of a curved surface or a complicated uneven portion.

[0006]

According to the present invention, a base material layer containing a thermoplastic elastomer as a main component is melt extruded into a sheet shape, and one surface of the base material layer is provided with a urethane resin as a main component on an adhesive resin layer on the back surface. A coating sheet characterized in that a layered body in which layers are integrally formed by a coating method is supplied, a foam layer is supplied to the other surface, and the above three members are pressure-bonded so that the surface layer contacts the embossing roll. The manufacturing method is the gist of the invention.

The urethane resin in the present invention has rubber-like elasticity at room temperature and is plasticized at high temperature. Generally, as a rubber component (soft segment) having entropy elasticity in the molecule, polyether, polyester, As a segment of polycarbonate or the like, or a molecular restraint component (hard segment) for preventing plastic deformation, it has a segment composed of a urethane bond, and there are a straight-chain type and a cross-linking type.

Examples of materials for the urethane resin include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate,
Diisocyanates such as trimethylhexamethylene diisocyanate, polyester diols such as condensed polyester diols, lactone polyester diols and polycarbonate diols, diols such as polyether diols, ethylene glycol, 1,4-butane diol, hydroquinone diethyl ether And a chain extender, and if necessary, a catalyst such as dibutyltin laurate.

In the above-mentioned cross-linking type, the above-mentioned low molecular weight materials and polymer materials obtained by polymerizing these are used, and further, at least trifunctional isocyanate such as hexamethylene diisocyanate isocyanurate or trimethylolpropane adduct or melamine cross-linking is used. It consists of agents. When these crosslinking type urethane resins are used for the surface layer, the solvent resistance of the surface layer is improved. Further, when a urethane resin of aliphatic non-yellowing type is used for the surface layer as the isocyanate, the surface layer has improved durability such as weather resistance and heat resistance.

The surface layer of these urethane resins may be directly formed by the casting method, but the surface layer may be formed by polymerization using a polymerization catalyst at the time of forming the film by the casting method.

The urethane resin having a glass transition point (Tg) in the range of -50 to 20 ° C. can be preferably used. If the Tg is less than -50 ° C, the strength of the obtained sheet is not sufficient, and if it exceeds 20 ° C, the sheet becomes hard and a soft feel cannot be obtained. The urethane resin having a weight average molecular weight in the range of 20,000 to 3,000,000 can be preferably used. Weight average molecular weight is 20,000
If it is less than 0, the rigidity of the obtained sheet decreases, and
When it exceeds 10,000, the flexibility is impaired, and neither of them gives a desirable result.

The above-mentioned evaluation of flexibility is conducted according to JISK7215.
It is also made according to the A hardness specified in paragraph 5, and this A hardness is 5
Those in the range of 0 to 98 give preferable performance. Examples of the urethane resin include products manufactured by Nippon Polyurethane Industry Co., Ltd., product names Nipporan SH703 and 5037, products manufactured by Asahi Glass Co., Ltd., product names Ufine PN3429, products manufactured by Nippon Miractolan, product names Miractoran E990P, products manufactured by Dainippon Ink and Chemicals, Inc. Name T7890 etc. are mentioned.

Elastic particles may be contained in the surface layer. The elastic fine particles have a property of elastically recovering rapidly when opened after being deformed under pressure at room temperature, and examples thereof include polyurethane, acrylic-urethane resin, and styrene-isoprene copolymer.
Further, the shape thereof may be a spherical shape, or may be a random shape obtained by means such as freeze pulverization. The size of the elastic fine particles is preferably such that the maximum value of the particle size distribution (hereinafter, abbreviated as average particle size) is in the range of 1 to 100 μm, and when the average particle size is less than 1 μm, the obtained sheet surface is The generated concavo-convex pattern does not clearly appear in a suede tone, and a so-called soft touch feeling cannot be obtained. Further, when the thickness exceeds 100 μm, the surface of the obtained sheet becomes rough, and in particular, the sheet surface is likely to be cracked in the stretching step performed to improve the surface property in the sheet manufacturing process. , Neither is preferable.

Further, the blending amount thereof is preferably in the range of 30 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic urethane elastomer. When the compounding amount is less than 30 parts by weight, the concavo-convex pattern generated on the surface of the obtained sheet does not appear clearly, and when it exceeds 150 parts by weight, the surface of the obtained sheet becomes a rough surface, and cracks are formed on the sheet surface in the stretching step described above. It is not preferable because it tends to occur. Further, the elastic fine particles may be used alone, or two or more kinds may be mixed and used. Furthermore, to give a slightly stiff feel,
Hard beads such as crosslinked polymethylmethacrylate or silica gel may be mixed and used in the elastic fine particles.

If necessary, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers, hindered amines, etc. may be added to the above-mentioned components constituting the surface layer of the coating sheet of the present invention. Further, a pattern such as printing may be applied to the front surface or the back surface of the surface layer to enhance the designability of the coating sheet of the present invention.

An adhesive resin layer is provided on the back surface of the surface layer. As the material for forming the adhesive resin layer, the most suitable adhesive material is selected and used depending on the type of the base material layer. When the base material layer is a polyolefin resin elastomer, chlorinated polyolefins, ionomer resins such as ethylene methacrylic acid copolymer metal salts,
Acid-modified SBS (styrene / butadiene / styrene copolymer), acid-modified SEBS (styrene / ethylene / butadiene / styrene copolymer) and the like are used.

The thermoplastic elastomer in the present invention is
A material having an A hardness defined by JIS K7215 in the range of 50 to 98 gives preferable performance. As the thermoplastic elastomer, for example, the above-mentioned thermoplastic urethane elastomer and other styrene-based, polyamide-based,
Polyester-based and polyolefin-based elastomers can be appropriately selected and used. Among them, polyolefin-based elastomers excellent in moldability and cost, having polypropylene as a hard segment and ethylene as a soft segment (EPM), Those having a diene component together with ethylene (EPDM), those obtained by mixing the above two, and those partially crosslinked with an organic peroxide are preferably used.

The above-mentioned thermoplastic elastomer improves the extrusion formability of the base material layer and the vacuum formability of the coating sheet.
For example, a polyolefin resin such as polypropylene or LLDPE (linear low-density polyethylene) may be added. The thermoplastic elastomer, which is the main component of the base material layer of the coating sheet of the present invention, has the above-described constituent components,
Further, if necessary, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers and hindered amines may be added.

Further, the urethane resin or the thermoplastic elastomer constituting the surface layer or the base material layer in the present invention is further provided with a conductive material, a photochromic compound, a dew condensation preventing agent, a rust preventive, an antibacterial / mold preventing agent. , With matting agents,
It is possible to give necessary properties or functions.

In the covering sheet of the present invention, a foam layer having heat insulating properties and cushioning properties is provided on the surface of the base material layer opposite to the surface layer laminated. Materials for forming the foam layer include polyolefin resins such as polypropylene and polyethylene, polystyrene, styrene resins such as styrene / maleic anhydride copolymers, polyurethane resins, polyvinyl chloride resins, and various other thermoplastic resins. Examples thereof include foams such as elastomers. In particular, when the foam has thermoformability, it can be used for a wider range of purposes. The expansion ratio of the foam is desired to be selected according to the use of the coating sheet of the present invention, but in general use, it is about 5 to 50 times.
Further, the base material layer and the foam layer may be directly laminated by a thermal bonding method, but as in the case of laminating the surface layer and the base material layer, the adhesive resin layer is used as the base material layer and the foam material. It may be provided between two layers.

The thickness of the coating sheet of the present invention varies depending on its application, but if the appearance of a suede-like soft touch feeling and the sheet formability are taken into consideration, the surface layer has a thickness of 5 to 100.
μm, base material layer 0.2 to 3 mm, foam layer 1 to 3 m
m, and the adhesive resin layer is preferably in the range of 5 to 100 μm.

The covering sheet of the present invention has the above-mentioned constitution, and its manufacturing method will be described. First, a laminate in which a surface layer containing a urethane resin as a main component is integrally formed on the adhesive resin layer on the back surface by a coating method is manufactured. This laminate is obtained by forming an adhesive resin layer into a sheet by an appropriate method such as an extrusion molding method, and then,
A solution obtained by dissolving the composition containing the urethane resin as a main component in a solvent is applied to one surface of the sheet by using a coating device such as a knife coater, a bar coater, a reverse roll coater or an air sprayer, and dried to be long. Being rolled up.

Next, the thermoplastic elastomer forming the base material layer is extruded into a sheet shape, and while the sheet is in a molten state, one surface of the sheet is laminated with the adhesive resin layer on the surface layer laminate. It is fed so as to be adhered between the material layer and the surface layer, and similarly, the foam layer is fed to the other surface of the sheet in the form of a sheet, and the above three members are sandwiched between a pair of embossing rolls at that portion. At the same time as the transfer and embossing of the surface layer, a covering sheet in which the surface layer, the adhesive resin layer, the base material layer and the foam layer are firmly bonded can be obtained.

[0024]

In the method for producing a covering sheet according to the present invention, a surface layer containing a urethane resin as a main component is integrally formed on the surface of the adhesive resin layer by a coating method. In the method, a composition containing a thermosetting urethane resin as a main component, which is difficult to use, can be used as a surface layer, and while having a sufficient matte and good suede-like feel,
A surface having excellent scratch resistance and solvent resistance can be formed. Further, the thermoplastic elastomer forming the base material layer is extruded into a sheet, and while the sheet is in a molten state,
The surface layer laminate is fed to one surface of the sheet so that the adhesive resin layer is bonded between the base material layer and the surface layer, and similarly, the foam layer is fed to the other surface of the sheet in a sheet form. ,
By pressing and transporting the above three members between a pair of embossing rolls in the portion, it is possible to very easily emboss the surface layer clearly and at the same time,
The adhesive resin layer, the base material layer and the foam layer can be firmly bonded.

In the present invention, the reason why the fine concavo-convex pattern can be embossed extremely easily as described above depends on the material constituting the coating sheet of the present invention and the combination thereof. It is inferred that the surface layer is heated from the central portion of the laminate when it is pressed and transferred. Further, the surface layer includes a base material layer containing a thermoplastic elastomer as a main component through an adhesive resin layer, and a foam layer on the other surface of the base material layer, while the base material layer is in a molten state. By forming a laminated structure, it is possible to provide a covering sheet having a good feel, scratch resistance, solvent resistance and the like.

[0026]

Embodiments of the present invention will be specifically described below with reference to the drawings, but the present invention is not limited thereto.

In the following examples, the appearance and scratch resistance were tested and evaluated by the methods shown below. 1. Appearance The obtained coating sheet was visually observed and evaluated whether or not the shape of the embosses formed on the surface layer was sharp, and evaluated in good condition.
The embossing roll used has a bottom surface of 0.5 mm and a top surface of 1.
mm, height 0.1 mm, inverted conical trapezoidal hole and bottom 1 m
A frustoconical protrusion having a height of 0.5 mm, a top surface of 0.5 mm, and a height of 0.1 mm is uniformly engraved on the entire surface in a staggered manner. The cross section of the surface layer of the obtained covering sheet was observed with a microscope to find the height of the grain at 1
It was measured at 0 points and shown as the average value.

2. Scratch resistance A load of 500g to 50g by a scratch strength test with a Taber clutch tester (manufactured by Toyo Seiki Seisakusho)
The maximum load, which was reduced every time and was not scratched, was measured visually, and a maximum load of 300 g or more was evaluated as good.

Example 1 Maleic acid-modified polypropylene (Adonor QF551 manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used as a material for the adhesive layer, and GT-40 (40φ, full flight, L / manufactured by Plastic Engineering Laboratory Co., Ltd.) was used. D = 26,
Compression ratio = 3) Extruder, coat hanger die (500 mm
Width) was used to mold a film having a width of 500 mm and a thickness of 20 μm at a mold temperature of 190 ° C. Then, on one surface of the film, chlorinated polyolefin (manufactured by Sanyo Kokusaku Pulp Co., Ltd., Super Clone 822; solid content 20%, chlorine content 24.
5%) was applied and dried to provide an undercoat layer having a thickness of 10 μm. Then, as a material for the surface layer, a urethane resin (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Nipporan SH7
03: Polycarbonate system, Tg = -20 ° C, solid content 3
0%, molecular weight 116,000, 100 parts by weight (as solid content), elastic fine particles (manufactured by Nippon Shokubai Kagaku Kogyo KK, EBS1)
00: Acrylic / urethane type, average particle size 10 μm) 10
0 parts by weight (as solid content) are mixed with stirring, and the above undercoat layer is coated with a comma coater, and the mixture is mixed at 80 ° C. for 10 minutes.
After drying for a minute, as shown in FIGS. 1 and 2, a laminate composed of the surface layer 1 and the adhesive resin layers 21 and 22 shown in the partially cutaway cross section was prepared as a long wound body.

The surface layer 1 is in contact with the surface of the laminate comprising the surface layer 1 and the adhesive resin layers 21 and 22 prepared as described above, and the surface of the embossing roll 51 having fine holes and projections. As described above, it was installed in the feeding device on the right side of FIG. Further, as a material forming the foam layer, a foamed polypropylene sheet (manufactured by Sekisui Chemical Co., Ltd., Softlon SPV2
502; foaming ratio 25 times, thickness 2 mm, width 500 mm)
1 was prepared and installed in the feeding device on the left side of FIG.

Next, as a material for forming the base material layer, 50 parts by weight of a thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Industry Co., Ltd., Mirastomer 8030N), a thermoplastic polyolefin-based elastomer (Mitsui Petrochemical Industry Co., Ltd., Mirastomer 5030N). 30 parts by weight, LLDPE
(Ultzex 2021L, manufactured by Mitsui Petrochemical Industries, Ltd.)
10 parts by weight, polypropylene (manufactured by Mitsui Petrochemical Industries,
10 parts by weight of high pole F650), all of which are in the form of pellets are mixed in a blender, and GT-50 (50φ, full flight, L / D = 2) manufactured by Plastic Engineering Laboratory Co., Ltd.
6, compression ratio = 3) extruder, coat hanger die (500m
m width) at a mold temperature of 230 ° C. and extruded into a sheet having a width of 500 mm and a thickness of 400 μm, and at the same time, the surface layer 1
The laminated body including the adhesive resin layers 21 and 22 and the expanded polypropylene sheet are fed from the left and right feeding devices, and the surface temperature of the three sheets is 50 at a position where the material forming the base material layer is in a molten state. The embossing rolls 51, which were cooled to 0 ° C., were pressed and transferred, and the above layers were firmly laminated to obtain a covering sheet in which the surface layer was embossed with a fine uneven pattern. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

Example 2 A urethane resin (Nipporan 503, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as a material for the surface layer.
7: Polyester type, solid content 45%, molecular weight 60,000
0) 100 parts by weight (as solid content), isocyanate (manufactured by Nippon Polyurethane Industry Co., Coronate HL; solid content 75%) 10 parts by weight (as solid content), dibutyltin dilaurate (curing catalyst) 0.5 parts by weight, elasticity A stirring mixture of 80 parts by weight (as solid content) of fine particles (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., EBS300; acrylic urethane type, average particle size 10 μm, solid content 50%) was used, and the surface layer had a thickness of 30 μm. The thickness of the material layer was changed to 350 μm, and a covering sheet was obtained in the same manner as in Example 1. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

Example 3 As a material for the surface layer, urethane resin (Nipporan SH7 manufactured by Nippon Polyurethane Industry Co., Ltd.) was used.
03: Polycarbonate system, Tg = -20 ° C, solid content 3
0%, molecular weight 116,000, 100 parts by weight (as solid content), elastic fine particles (manufactured by Nippon Shokubai Kagaku Kogyo KK, EBS1)
00: acrylic / urethane type, average particle size 10 μm, solid content 44%, 70 parts by weight (as solid content), porous inorganic material (Fuji Davison Chemical Co., Ltd., Cyloid 244; average particle size 1.8 μm, oil absorption 310 ml / 100 g) using 10 parts by weight of the stirred mixture, the surface layer having a thickness of 50 μm,
The thickness of the adhesive resin layer is 30 μm, and the thickness of the base material layer is 1.0
The coating sheet was obtained in the same manner as in Example 1 except that the thickness was changed to 00 μm. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

Example 4 As a material for the surface layer, a urethane resin (polyester type, OH group value = 20, solid content 20)
%, Molecular weight 100,000) 100 parts by weight (as solid content), isocyanate (Nippon Polyurethane Industry Co., Ltd., Coronate HL; solid content 75%) 10 parts by weight (as solid content), dibutyltin dilaurate (curing catalyst) 0.1. 5 parts by weight, elastic fine particles (manufactured by Dainippon Ink and Chemicals, Inc., Burnock CFB101-40; urethane type, average particle size 8 μm
m, solid content 50%) 80 parts by weight (as solid content) of the agitated mixture, the thickness of the surface layer was changed to 30 μm, and the thermoplastic polyolefin elastomer (Mitsui Petrochemical Industry Co., Ltd.) was used as the base material. Made by Mirastomer 8030
N) 80 parts by weight, LLDPE (Mitsui Petrochemical Industry Co., Ltd.,
Ultzex 2021L) 10 parts by weight, polypropylene (Mitsui Petrochemical Co., Ltd., Hipol F650) 10
All parts by weight were pellets mixed with a blender, the thickness of the base material layer was changed to 500 μm, and a coating sheet was obtained in the same manner as in Example 1. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

(Comparative Example 1) A covering sheet comprising only a base material layer and a foam layer without the surface layer of the present invention was obtained in the same manner as in Example 1. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

(Comparative Example 2) The thickness of the surface layer was changed to 50 μm, and as a material for the adhesive resin layer, chlorinated polyolefin (Sanyo Kokusaku Pulp Co., Ltd., Supercron 822; solid content 20%, chlorine content 24) 0.5%), the thickness of the adhesive resin layer is changed to 10 μm in diameter, and the thickness of the base material layer is changed to 35 μm.
The thickness was changed to 0 μm and a covering sheet was obtained in the same manner as in Example 1. The appearance and scratch resistance of the obtained covering sheet are shown in Table 1.

[0037]

[Table 1]

[0038]

According to the method for producing a covering sheet of the present invention, a surface layer containing urethane resin as a main component is integrally formed on the surface of the adhesive layer by a coating method. Then, a composition containing a thermosetting urethane resin as a main component, which is difficult to use, can be used as the surface layer,
A surface layer excellent in scratch resistance, solvent resistance and the like can be formed while having a sufficient matte and good suede-like feel. Further, the thermoplastic elastomer forming the base material layer is extrusion-molded into a sheet shape, and while the sheet is in a molten state, the surface layer laminate is provided on one surface of the sheet and the adhesive resin layer forms a surface with the base material layer. It is fed so as to be adhered between the layers, and similarly, the foam layer is fed to the other surface of the sheet in the form of a sheet, and at the portion, the three sheets are conveyed while being sandwiched between a pair of embossing rolls. This makes it possible to very easily emboss the surface layer clearly and at the same time firmly bond the surface layer, the adhesive resin layer, the base material layer and the foam layer. Further, the surface layer has a structure in which a base material layer containing a thermoplastic elastomer as a main component through an adhesive layer and a foam layer are integrally laminated on the other surface of the base material layer, thereby providing a good feeling and It is possible to provide a coating sheet having scratch resistance, solvent resistance and the like.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view schematically showing an example of an apparatus suitable for carrying out the method for producing a coating sheet of the present invention.

FIG. 2 is a sectional view taken along line II-II in FIG.

3 is a sectional view taken along line III-III in FIG.

[Explanation of symbols]

 1 Surface Layer 21 Adhesive Resin Layer 22 Undercoat Layer 3 Base Material Layer 4 Foam Layer 51 Embossing Roll

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/40 7421-4F 31/12 7148-4F 31/20 7148-4F // B29K 21:00 75:00 105: 04 B29L 9:00

Claims (1)

[Claims] 1. A base material layer containing a thermoplastic elastomer as a main component is melt-extruded into a sheet, and a surface layer containing a urethane resin as a main component is integrally formed on one surface of the base material layer on an adhesive resin layer on the back surface by a coating method. The method for producing a covering sheet, comprising supplying the laminated body, supplying a foam layer to the other surface, and crimping the above three members so that the surface layer contacts the embossing roll.